Textile dye carrier emulsifier composition and process for dyeing polyesters therewith

ABSTRACT

A LIQUID DYE CARRIER COMPOSITION INCLUDING BY WEIGHT ABOUT 60 TO ABOUT 100% OF A NORMALLY LIQUID ALKYLATED BIPHENYL, ABOUT 40 TO 0% BIPHENYL AND ABOUT 5 TO ABOUT I/% OF ANIONIC AND/OR NONIONIC EMULSIFIERS BASED ON THE WEIGHT OF THE ALKYLATED BIPHENYL. THE LIQUID ALKYLATED BIPHENYL MAY BE EMPLOYED ALONE OR AS A LIQUID ISOMERIC MIXTURE IN A DYE BATH FOR DYEING POLYESTER FIBERS AND OTHER ARTICLES HAVING A SYNTHETIC POLYMER OR OTHER BASIS.

United States Patent O TEXTTLE DYE CARRIER EMULSIFIER COMPOSI- TION AND PROCESS FOR DYEING POLYESTERS THEREWITH Ben N. Freshwater, Chattanooga, and Robert C. Goodrich, Signal Mountain, Tenn, assignors to GAF Corporation, New York, N.Y. No Drawing. Filed Oct. 18, 1971, Ser. No. 190,163

Int. Cl. D061: 1/68 US. Cl. 8-174 11 Claims ABSTRACT OF THE DISCLOSURE A liquid dye carrier composition including by weight about 60 to about 100% of a normally liquid alkylated bi henyl, about 40 to biphenyl and about to about 20% of anionic and/or nonionic emulsifiers based on the weight of the alkylated biphenyl. The liquid alkylated biphenyl may be employed alone or as a liquid isomeric mixture in a dye bath for dyeing polyester fibers and other articles having a synthetic polymer or other basis.

BACKGROUND OF THE INVENTION This invention relates to a novel composition which is a useful aid in dyeing of fibers, and to a dyeing process employing such composition. More specifically, this invention relates to a novel liquid dye carrier-emulsifier composition useful in aiding the dyeing of synthetic fibers by either pressure or non-pressure dyeing. Still more specifically the invention relates to a textile dye carrier-emulsifier composition which may be used with dyes of the dispersed or acetate class, these dyes being especially useful in dyeing fibers which are hydrophobic, such as polyester blends, cellulose triacetate, and the like.

Synthetic textile fibers which are hydrophobic, especially polyester and cellulose triacetate, are particularly difficult to dye and cannot satisfactorily be dyed by ordinary procedures such as those used for dyeing cotton, wool, silk, regenerated cellulose, and the like. When ordinary dyeing procedures are used for dyeing hydrophobic synthetic organic materials, the dye does not penetrate the material to any appreciable extent and either no dyeing is obtained, or if some measure of dyeing is obtained, the color is not fast and thus washes out of the material thereby making the dyeing of such materials quite difficult.

Prolonged dyeing procedures are obviously unsuitable for continuous dyeing (for instance, dyeing of piece goods) and furthermore are costly with respect to both time and energy consumed. Moreover, the heating of polyester fibers at high temperatures for prolonged periods tends to injure the fiber through hydrolysis or has other adverse chemical and/or physical effects. Attempts to improve the dyeing of the above fibers with assistants and carriers have in the past often lead to unsatisfactory results, such as plasticizing or shrinking the fibers or imparting thereto a harsh hand, and/or degrading the fastness of the dyes. The use of dispersed dyes does not always solve the problem inasmuch as dispersed dyes have poor dispersibility and slow wet-out in cold water, both of which are disadvantageous since ease of dispersibility and rapid wet-out in cold water permits easier and more rapid handling by the dyer.

A further disadvantage with certain dispersed dyes is that if the dye is poorly dispersed it is difiicult to filter, especially if drying is to be performed in separate equipment and it is therefore sometimes dificult to transfer the dyepaste to the drying equipment.

Several processes using non-aqueous solvent media have in the past been proposed for the purpose of decreasing the dyeing time, but the temperature required 3,728,078 Patented Apr. 17, 1973 ice of these solvents is high, in the range of 265 F. to 390 F. At these temperatures many dispersed dyes decompose and it has in the past been necessary to add a dye stabilizer to the dye bath, also, these methods introduce additional costs and the problem of removing the solvent from the dyed fibers.

The use of known carriers or swelling agents has sometimes been successful with the dispersed or acetate types, however, since these dyes have a very limited solubility in water, it is necessary to disperse the dyestuff in the dye bath in the form of finely-divided solid particles in order to effect dyeing. Since the carrier is operative to form or open deep pores in the hydrophobic materials it permits the dye to enter and remain there in a color-fast manner, but the known carriers have their attendant drawbacks, thus limiting their use.

The dye carriers which have heretofore been used in conjunction with dispersed dyes are usually water-insoluble materials which also must be emulsified or in some way suspended in the dye bath. These carriers are believed to function in two ways: (1) by partially swelling the fibers to facilitate penetration and diffusion of the dye into the fiber, and (2) by acting as a solvent for the dye, and thus reducing the agglomerated dye particles to a size which can more readily penetrate the fiber.

Many chemical compounds and compositions have been developed as assistants or carriers for the dyeing of hydrophobic materials; many of these are phenols or phenolic derivatives which are acidic and corrosive in nature and consequently are not completely satisfactory or acceptable to industry. Additionally, these compounds decrease light fastness and introduce persistent objectionable odors into the dyeing process which often remain behind in the dyed materials. Other dye carrier compositions including chlorinated hydrocarbons, are like the phenolics, toxic and irritating, flammable and/or combustible, or are expensive and uneconomical and accordingly are not completely acceptable to industry.

As representative of some of the objectionable phenolic dye carriers there may be mentioned the following: 0- phenylphenol, p-phenylphenol, o-dichlorobenzene, trichlorobenzene, monochlorobenzene, diphenyl, ethyl silicylate, butyl benzoate, benzoic acid and the like. The foregoing carriers are unsuitable for the reasons mentioned and some are solids to which the mill must of necessity add and often provide a solvent so that the final dye carrier-emulsifier product is a liquid. Generally, in those instances, a compound which is also a known dye carrier may be used as the solvent. For example, trichlorobenzene, toluene, butyl benzoate or methyl silicylate may be used as solvents for biphenyl, the latter being a solid dry flaked or granular dye carrier.

Some unacceptable dye carriers which are presently available must be dissolved in sodium hydroxide solution prior to addition to the dye bath, and thereafter must be precipitated as a fine dispersion by the addition of acetic acid. This procedure is difficult, is time consuming, limits the pH of the dye bath and lastly, the resulting dispersion is not stable. If the dye bath is not used promptly the dispersed droplets of carrier will coalesce, forming larger drops which cause spotty dyeing. Dye carriers may also be emulsified in a dye bath by means of surface active agents, the resultant formation of a stable aqueous dye bath emulsion often helps to overcome the problem of spotty dyeing, but not the other aforementioned drawbacks. The dye carriers which are generally used in disperse dyeing processes have limited water solubility (the dyestuffs are also water-insoluble), therefore, it is necessary to add emulsifiers to the aqueous dye baths in order to disperse or emulsify the carrier (and the dyestufi) in the bath.

Textile mills prefer to use a ready made non-toxic, non-combustible, liquid product containing both a dye carrier and an emulsifier. Some commercially available dyecarrier-emulsifier compositions perform well as dye carriers but suffer from the following disadvantages: (1) they are grainy pastes and therefore, very difficult to handle and measure; (2) they are not too readily dispersed in water and generally require that the dispersion be boiled; (3) their aqueous dispersions are not stable, therefore requiring that the dispersion be pre-prepared and added to the dye bath immediately before dyeing in order to avoid separation; and (4) they must be used at relatively high concentrations in order to obtain a given dye shade.

The novel liquid carrier composition of the instant invention is particularly adapted to be used with any dyestuif, dispersed or otherwise, and is particularly suitable'for use in the dyeing of polyester fibers such as condensation polymers of ethylene glycol and terephthalate acid known in the trade as Dacron, Terylene, Fortrel and the like, modified acrylic fibers of which a trade example is Verel, polymers comprising vinylidene dinitrile as their basic constitutent, such as 'Darlan, cellulose triacetate of which a trade example is Arnel, and various other thermoplastic and thermosetting polymers, all of which may be in fiber, film or other solid shape. Moreover, the carrier composition of this invention is also adapted for use in dyeing modified polyester fibers such as Dacron Type 62 or 64 with cationic dyestuffs which contain positively charged nitrogen group within the molecule and which may be dispersed or dissolved in water with the aid of acids, such as acetic or formic acids.

SUMMARY OF THE INVENTION It is accordingly an object of the instant invention to provide a novel liquid dye carrier composition which is suitable for use in dyeing the above described hydrophobic synthetic fibers.

It is another object of the instant invention to avoid one or more of the drawbacks of the prior art.

It is still another object of the present invention to provide a liquid dye carrier composition which is substantially non-toxic, non-flammable and yet is effective in dyeing hydrophobic synthetic fibers.

It is still another object of the instant invention to reduce the amount of time necessary in dyeing such synthetic fibers by the beck, jug, paddle, patter, package machine, and other dyeing methods.

It is a further object of the invention to provide a dye carrier composition which is readily dispersible or emulsifiable in water.

It is yet a further object of the invention to provide a dye carrier composition which forms stable aqueous emulsions.

Other objects and advantages of the instant invention will be apparent to those skilled in the art from the following description.

It has unexpectedly been found that the instant invention which may include an alkylated biphenyl alone or a mixture thereof with solid biphenyl produces a liquid carrier which is operative to avoid one or more drawbacks of the prior art, especially those associated with the liquid type carriers that are presently available (U.S. Pats. 3,097,047; 3,203,753 and 3,057,674). Broadly speaking, the instant invention includes the provisions of a liquid dye-carrier composition consisting essentially of by weight about 60 to about 100% of a normally liquid alkylated biphenyl, about 40 to biphenyl and about 5 to about 20%, based on the weight of the alkylated biphenyl, of at least one agent selected from the group consisting of anionic and nonionic emulsifiers. Preferably the composition contains about 65 to about 75% of said alkyl substituted biphenyl (or an isomeric mixture thereof) and about 8 to about 12% of said emulsifiers based on the weight of said alkylated biphenyl.

The liquid alkylated biphenyl may be mono or dialkyl substituted in any one or two of the 2, 3 or 4 carbon positions of one or both rings, said alkyl containing 1-3 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl. Substantially the only essential feature is that the alkylated biphenyl or isomeric mixture thereof, with the biphenyl when employed, is liquid at ambient temperatures, e.g., room temperature or about 10-30" C. Preferably the alkylated biphenyl is mono-methyl biphenyl.

Still more preferably, the mono-methyl biphenyl 'is an isomeric mixture, optimally a mixture consisting essentially of about 20% ortho, 40% meta and 40% para isomers, by weight, alone or still more preferably combined with biphenyl in the percentages as stated above. The product thus obtained is made self-emulsifying and water dispersible at temperatures of from about 20 to about 300 F., without the mill needing to heat the solid biphenyl first in order to make it so. A variety of standard emulsifiers added in amounts of from about 5% to about 20% by weight have been found to be effective.

it has been found that the instant dye carrier-emulsifier composition is particularly effective for dyeing fibers with dispersed, and also cationic, dyes from an aqueous dye bath. It has also been found that since the composition is a liquid it provides ease of handling and measuring, and also facilitates dispersion or emulsification in the dye bath.

When the carrier-emulsifier composition is used in dyeing fibers, it should be employed in amounts of about 1 to about 20% by weight of the fibers to be dyed.

The dye carrier component generally acts as a chemical assistant for the dispersed dye by promoting penetration and sorption of the dyestulf into the textile. The carrier also generally aids in producing an intimate contact between the textile fiber and the dyestuff, and its function may be affected by such factors as the nature of the fiber, the nature of the dyestuff, the dyeing medium and the like. In general, dye carriers should be cheap, functional and be easily removable from the fiber after dyeing in order to prevent possible adverse effects on light fastness. The dual emulsifier component herein, when'employed, performs several functions in the dispersed dyeing operation. It has been found that very good emulsion stability is achieved by combining with the dye carrier the anionic and nonionic emulsifiers and thereafter adding them to the same dye bath. As previously indicated, the emulsion which is formed comprises a dyestuif-carrier-in-water emulsion. When both the anionic and nonionic emulsifiers are present in the dye bath, the emulsion will remain stable for several hours, thus eliminating the necessity of preparing the emulsions immediately prior to the dyeing, though it is preferable not to let the emulsion stand too long before use. In addition, the formation of a stable emulsion enchances dyeing.

The term fiber" is used herein to include filaments, fibers, bristles, frills, flakes, fabrics and the like, which have been produced from the above described polymers. The term dyestuif as uesd herein includes dyestuffs of both the dispersed and cationic types.

The dispersed types dyestuffs which may be used for the purpose of this invention include the azo, nitroarylamine or anthraquinone compounds. Specific examples of such type dyestuff are:

1,4-diamino 2,3 anthraq-uinone dicarboximide (blue crude dispersed dyestufi); l,4,5,8-tetramino anthraquinone (blue crude dispersed dyestuif); 1,4-dialkylamino anthraquinone (blue crude dispersed dyestuff); 2,6-dichloro-4- nitro-4'-(N,N hydroxyethyl methyl) amino-azobenzene (brown crude dispersed dyestuff); 4-nitro-4' (N,N-hydroxyethyl-ethyl) amino azobenzene (scarlet crude dispersed dyestutf); 4,4'-dia'mino-azobenzene (orange crude dispersed dyestuff); l-hydroxy-4 amino anthraquinone (red crude dyestuff); the Genacron and Celliton dyes series (GAF Corporation) and the like.

The dispersed dyestuffs are generally used in commercially available compositions which contain from about 10 to about 40% of the crude dyestuffs. These dispersed type dyestuffs when employed with the composition of the instant invention may be added directly to the dyeing bath to which will be added the composition of the instant invention.

An exemplary list of cationic dyes which may be empolyed with the composition of the instant invention is as follows:

Color AATCC prototype index 25 Dye designation No.

Genacryl Red 4B Basic Violet 16 48013 Genacryl Blue 3G Basic Blue 3 51005 Genaeryl Blue B. Basic Blue 5. 42140 Genacryl Orange G Basic Orange 21 48035 Genacryl Orange R Basie Orange 22 48040 Genaeryl Pink 3G. Basic Red 14.-. Genacryl Pink G Basie Red 13.. 48015 Genaeryl Yellow 4G Basie Yellow 11 48055 Genaeryl Brilliant Red B Basic Red 15 Victoria Green S Ext. Cone Basie Green 4 42000 Sevron Yellow L Genacryl Yellow 5GF Astrazon Orange G Rhodamine B Basic Orange 21 Basic Violet 10.

Basic Yellow 11 Sevron Brilliant Red 4G Basic Red 14 Sevron B e B Basie Blue 21 Sevron Blue 2G. Basic Blue 22 Basic Blue 1 42025 Basic Violet 7 48020 The above list is representative of those cationic dyestuffs that can be advantageously employed with carrier compositions of the present invention. It is of course to be understood that any suitable cationic dye that is advantageously employed in the dyeing of fibers and fabrics and particularly synthetic fibers and fabrics can be advantageously employed.

DETAILED DESCRIPTION The composition of the instant invention is particularly advantageous since it permits fine dispersions throughout the dye bath so that all portions of the material to be dyed will receive a fair distribution of the dyestuif. In addition, the emulsifying or dispersing agent generally places the alkylated biphenyl in a condition which permits quicker and more uniform distribution thereof in the dye bath. It has been found that good results are obtained when the monoalkylated biphenyl carrier is employed in amounts of about 1 to about 20%, preferably about 312% for non-pressure and about 2 5% for pressure dyeing by weight, based on the weight of the fiber to be dyed (OWG). However, in non-pressure dyeing the exact amount of carrier to be used will to a great extent depend on whether or not the goods are to be dyed to a light, medium or heavy shade. When it is desired to dye the goods to a light shade, it is preferred to use about 5% CW6 of the carrier, and when the goods are to be dyed to a medium shade, it is preferred to use about 7% of the carrier, and for heavy shades it is preferred to use about 10% of the carrier. In pressure dyeing, the amount of carrier used is not critical with respect to shade.

The emulsifying agents employed are, as stated, generally surface active agents of the anionic or nonionic type, and the emulsifying agent either alone or in combination (both anionic and nonionic) is generally mixed with the carrier to the extent of about 5 to 20%, preferably about 8 to about 12%, based on the weight of the carrier.

The anionic and nonionic emulsifiers perform other functions in addition to forming the aforesaid emulsions. For example, the anionic emulsifier is believed to affect the efficiency of the instant composition as a dye carrier, and believed to promote deposition of the emulsified droplets of carrier on the fabric during the dyeing, resulting in improved efficiency of dyeing. The nonionic emulsifier is believed to also function as a leveling agent for the dispersed dyes which helps promote uniform (level) dyeing.

-In addition to the particular types of emulsifiers which are used in combination, the ratio of the two emulsifiers (anionicznonionic) and the total amount of emulsifier used also affects the aqueous emulsion stability and the quality of the dyeing. The ratio of anionic-to-nonionic emulsifier is preferably selected so as to give optimum, aqueous emulsion stability and dyeing characteristics. In general, the ratio which will form a stable emulsion will fall within a range of from about 10:90 to about :10 by weight, though the ratio yielding optimum emulsion stability such as about 40:60 will vary within this range depending upon the particular anionic and nonionic emulsifiers which are used. It is a relatively easy matter to vary the anionic-nonionic ratio to determine optimum aqueous emulsion stability and dyeing characteristics. Emulsifier ratios outside of the above ranges may cause poor emulsion stability, poor (spotty) dyeings, or dyeings that are too light in shade to be practical.

The typical emulsifying agents referred to below are disclosed in US. Pats. 3,097,047 and 3,203,753 and said patents are incorporated herein by reference. They may be represented by the following formulae; in which R designates an alkyl group and M is a metal salt such as sodium, potassium, ammonium, or a derivative of ammonia or the like.

( 1 RCOOM wherein R is an alkyl group containing 8 to 24 carbon atoms.

( ROSO OM wherein R is an alkyl group containing 8 to 24 carbon atoms.

( RSO3M wherein R is an alkyl group containing 12 to 18 carbon atoms.

4 RAr-SO M wherein R is an alkyl group containing 3 to 18 carbon atoms and Ar is an aromatic m nucleus selected from benzene, naphthaline, anthracene or the like.

wherein R is an alkyl substituent on a benzene ring containing 1 to 18 carbon atoms and Ar is a benzene nucleus and n is at least 1 and high as 10.

wherein R is an alkyl group containing 1 to 18 carbon atoms, Ar is a benzene nucleus and n is a number from 4 to 40.

wherein R is an alkyl group containing 8 to 24 carbon atoms and n is a number from 4 to 40.

wherein R is an alkyl group containing 8 to 24 carbon wherein R is an alkyl or amido group containing 8 to 24 carbon atoms; R is hydrogen, alkyl or aralkyl group; R is hydrogen or an alkyl group containing 1 to 8 carbon atoms, R is hydrogen alkyl or aralkyl group and X is an anionic radical, e.g., fluoride, sulfate or sulfate derivative. The type of emulsifying agents specified above are well known to those skilled in the art and any one of them or mixtures thereof can be used for the composition of this invention. For example, various classes are included such as sulfonated castor oil, sulfated alcohols, alkyl sulfonates, alkaryl sulfonates, sulfated ethoxylated alkyl phenols, ethoxylated alcohols, sulfated ethoxylated alcohols, ethoxylated fatty acids and the like. Specific examples of emulsifying agents are lauryl dimethyl benzyl ammonium chloride, Turkey red oil, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, sodium tetraethoxylated diisobutyl phenol sulfate and the like. A detailed description of anionic and nonionic emulsifiers useful in the instant invention may be found in Surface Active Agents, by Anthony M. Schwartz and James W. Perry, Interscience Publishers, Inc., New York, N.Y., p. 151- 214 (1949).

Though it is preferred that the dye carrier and the emulsifier be blended into an easily handled liquid prior to addition to the dye bath, the separate addition of dye carrier, anionic and nonionic emulsifier to the dye bath is within the scope of this invention. Generally, the dye carrier plus one or both or mixtures of anionic and nonionic emulsifiers will constitute from about 1 to about 20 weight percent of the fabric to be dyed, though this is a matter of the operators choice and depends on the shade to which the fabric is to be dyed.

The amount of dispersed or cationic (basic) dye used will to a great extent depend on the shade required and upon factors well understood in the dyeing art.

Conventional disperse dyeing techniques may be employed when using the novel dye carrier emulsifier composition of this invention. At atmospheric pressure (nonpressure dyeing) the disperse dyestuff may be added to the aqueous dye bath either before or after the dye carrier and emulsifiers are added. A typical dyeing procedure which may be employed includes adding to an aqueous dye bath at a temperature of about 110 F. to about 212 F., preferably about 150 to about 170 F., a quantity of the dye carrier-emulsifier composition sufiicient to provide from about 1 to about 20 weight percent of the dye carrier per weight of the material to be dyed. After the addition of the carrier and emulsifiers, the dyestuif may be added and the temperature of the bath slowly adiusted to the temperature desired for carrying out the dyeing, preferably about 180 F. to the boil. The pH of the dye bath should be adjusted to optimum conditions for dyeing, about 39, preferably 5-7, subsequent to the addition of the carrier-emulsifier composition. After the desired temperature is reached, the fiber is held in solution for a period of about one to about 2 hours. At the end of this time, the fiber is scoured in a fresh bath according to well known procedures.

On the other hand, Where dyeing is carried out under pressure, for example 100 p.s.i.a. the temperature may be at about 212 to about 350 F., the preferred range being 230-260 F. For either types of dyeing, the dye will be employed in amounts of about .1 to about 2% by weight of the fabric, on a solids basis.

The following examples are presented to further illustrate the composition and method of this invention and are not to be considered as limiting. As employed herein and in the appended claims, all parts and proportions are by weight unless otherwise specified. It is furthermore to be understood that the term consisting essentially of, as used in the claims is to be interpreted as covering the use of minor amounts of other, nonspecified ingredients. It will be understood that the details of the following examples may be varied by those having skill in the art, without however, departing from the scope and content of the instant invention. In these examples, the methyl biphenyl is preferably a mixture of mono-methyl isomers,

more preferably a mixture of about 20% ortho, 40% meta and 40% para isomers by weight.

EXAMPLE I A dye carrier-emulsifier composition according to the instant invention was prepared as follows.

Ingredient, Amount dye carrier: (weight percent) (65-75% methyl b1phenyl:35-25% biphenyl) l0 The ingredients were weighed out and mixed together with stirring. The mixture was gently warmed until substantially homogeneous. The composition remained clear when cooled to room temperature.

The dye carrier-emulsifier composition was thereafter stirred into a warm (about F.) aqueous dye bath containing about 2.5% OWG of Celliton Fast Yellow 4RL (Color Index No. 26070), a dispersed dyestuif. Three concentrations of dye carrier-emulsifier composition were tested: about 10% for heavy shades, about 7% for medium shades, and about 5% for pastel shades (percentage based on the Weight of the fiber to be dyed). The results indicated that the dye carrier-emulsifier composition was effective and produced uniform (level) dyeings on polyester and polyester blend fibers.

The above procedure is repeated using a Genacryl Red 4B cationic dye (Color Index No. 48013). The same good results are obtained.

Several other dye carrier-emulsifier compositions were prepared and tested for dyeing polyester fiber and polyester blends with the dispersed and cationic dyes as in Example I. The formulations used to prepare these compositions are presented in Table I. In each instance the remainder of the dye carrier is essentially biphenyl. The following code for the emulsifiers is used in Table I.

ANIONIC A=Isopropylamine salt of dodecyl benzene sulfonic acid B=Cocoanut acid ester of sodium of isethionate C=Oleic acid ester of sodium isethionate D=Sodium N-cyclohexyl-N-palmitoyltaurate E=S0dium N-methyl-N-oleoyltaurates F=Sodium N-cocoanut acid-N-methyltaurate G=Sodiurn N-methyLN-tallow acid taurate H=Sodium N-methyl-N-tall oil acid taurate I=Sodium N-methyl-N-palmitoyltaurate J =Sodium dodecyl benzene sulfonate K=Sodium salt of sulfated nonyl phenoxypoly (ethyleneoxy) ethanol L=Ammonium salt of sulfated nonyl phenoxypoly (ethyleneoxy) ethanol M=Ammonium salt of linear alphatic ethoxylate sulfates N==Sodium salt of sulfonated naphthalene formaldehyde condensates O=Sodium alkyl naphthalene sulfonates P=Sulfonated aliphatic polyesters Q=Sulfated castor oils R=Sulfated fatty acids S=Sodium salt of complex phosphate esters T=Free acid of complex phosphate esters NONIONIC A'=Octyl phenoxypoly (ethyleneoxy) ethanol B'=Nonyl phenoxypoly (ethyleneoxy) ethanol C'=Alkylphenoxypoly (ethyleneoxy) ethanol D=Dialkylphenoxypoly (ethyleneoxy) ethanol E=Dodecylphenoxypoly (ethyleneoxy) ethanol F'=Linear aliphatic ethoxylates G'=Branched chain aliphatic ethoxylates, e.g. (0x0) tridecyloxypoly (ethyleneoxy) ethanol H'=Alkylpoly (ethyleneoxy) glycol amide I=Modified aliphatic polyethers J=Modified linear aliphatic polyethers K=Polyethoxylated fatty acids L'=Polyoxyethylated vegetable oils M=Polyoxyethylated fatty alcohols N=Polyoxyethylenealkyl amines O'=Polyoxyethylene sorbitan fatty acid esters P'=Polyethoxylated fatty acid esters TABLE I Anionic Nonionie Example No. Dye carrier emulsifier emulsifier II Methyl biphenyl 88% 6% 'I 6% O' K v1 Methyl biphenyl 89% o 5% D VII Methyl biphenyl88% O 5% 2% L: vIII -.do o 32 5, 5% D IX .do o ig; g, 1% H 8% P X. Methyl biphenyl 92% 0 1% L 1% D 6% P XI ..d0 0 1% K 5% D XII do o .{fifi 4% T XIII d0 0 4% O 1% D 2.57 T XIV .-do o xv do o $313, XVI Methyl biphenyl 90% 5% A 5% K XVII Methyl biphenyl 92% 4% A 4% K: XVIII Methyl biphenyl 90% o ga XIX dn 0-. 1 XX do 5% A 5% P XXI -do 5% A 5% Q The results of dyeings assisted by formulations of Examples II to XXI are satisfactory using the instant carrier-emulsifier composition.

The principal advantages of the instant novel invention have already been pointed out. In addition, the dyeing process of this invention is adapted for using unstandardized dyes, that is, dyes to which no additives have been incorporated such as dispersing agents, surfactants or standardizing agents. The instant invention also eliminates the need to add additional carriers, leveling agents or dispersing agents to the dye bath,

We wish it to be understood that we do not desire to be limited to the exact details shown and described, for obvious modifications will occur to persons skilled in the art.

Having thus described the invention, what we claim as new and desire to be secured by Letters Patent, is as follows:

1. A liquid dye carrier composition consisting essentially of by weight at least about of a normally liquid alkylated biphenyl, no more than 40% biphenyl and about 5 to about 20%, based on the weight of the alkylated biphenyl, of at least one agent selected from the group consisting of anionic and nonionic emulsifiers.

2. A composition as defined in claim 1 wherein said alkylated biphenyl is an isomeric mixture.

3. A composition as defined in claim 2 containing about to about of said isomeric mixture of alkylated biphenyl.

4. A composition as defined in claim 1 containing about 65 to about 75 of said alkylated biphenyl.

5. A composition as defined in claim 1 wherein said alkylated biphenyl is monoalkylated.

6. A composition as defined in claim 1 wherein said alkylated biphenyl is polyalkylated.

7. A composition as defined in claim 1 wherein said alkylated biphenyl is methyl biphenyl.

8. A composition as defined in claim 1 wherein said emulsifier is included in an amount of about 8 to about 12% by weight of the alkylated bi henyl.

9. The process of dyeing synthethic polyester fibers and polyester blend fibers which comprises treating said fibers with a dye bath containing a dyestuff for said fibers and a carrier composition as defined in claim 1.

10. The process as defined in claim 9 wherein said carrier composition is employed in amounts of about 1 to about 20% by weight of the fiber to be dyed.

11. A composition as defined in claim 1, also including a dye selected from the group consisting of basic and disperse dyes.

References Cited UNITED STATES PATENTS 3,057,674 10/ 1962 Mussel et a1. 8-94 X 3,097,047 7/ 1963 Weinstein et al. 8l79 X 3,203,753 8/ 1965 Sherburne 883 3,617,213 11/1971 Britt 8--173 X GEORGE F. LESMES, Primary Examiner T. J. HERBERT, JR., Assistant Examiner U,S. c1, xn. 8-21 0, 94 

